CN104892887B - A kind of preparation method of multi-arm acrylate block copolymer - Google Patents

A kind of preparation method of multi-arm acrylate block copolymer Download PDF

Info

Publication number
CN104892887B
CN104892887B CN201510347178.8A CN201510347178A CN104892887B CN 104892887 B CN104892887 B CN 104892887B CN 201510347178 A CN201510347178 A CN 201510347178A CN 104892887 B CN104892887 B CN 104892887B
Authority
CN
China
Prior art keywords
block copolymer
arm
acrylate
preparation
monomer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Active
Application number
CN201510347178.8A
Other languages
Chinese (zh)
Other versions
CN104892887A (en
Inventor
李坚
刘新
孙仪琳
任强
汪称意
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Changzhou University
Original Assignee
Changzhou University
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Changzhou University filed Critical Changzhou University
Priority to CN201510347178.8A priority Critical patent/CN104892887B/en
Publication of CN104892887A publication Critical patent/CN104892887A/en
Application granted granted Critical
Publication of CN104892887B publication Critical patent/CN104892887B/en
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/6692—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/34
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6225—Polymers of esters of acrylic or methacrylic acid
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/633—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers onto polymers of compounds having carbon-to-carbon double bonds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/14—Methyl esters, e.g. methyl (meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/10—Esters
    • C08F120/12—Esters of monohydric alcohols or phenols
    • C08F120/16—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms
    • C08F120/18—Esters of monohydric alcohols or phenols of phenols or of alcohols containing two or more carbon atoms with acrylic or methacrylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F120/00—Homopolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride, ester, amide, imide or nitrile thereof
    • C08F120/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F120/42—Nitriles
    • C08F120/44—Acrylonitrile
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F293/00—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule
    • C08F293/005—Macromolecular compounds obtained by polymerisation on to a macromolecule having groups capable of inducing the formation of new polymer chains bound exclusively at one or both ends of the starting macromolecule using free radical "living" or "controlled" polymerisation, e.g. using a complexing agent
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/08—Processes
    • C08G18/0804—Manufacture of polymers containing ionic or ionogenic groups
    • C08G18/0819—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups
    • C08G18/0823—Manufacture of polymers containing ionic or ionogenic groups containing anionic or anionogenic groups containing carboxylate salt groups or groups forming them
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/34—Carboxylic acids; Esters thereof with monohydroxyl compounds
    • C08G18/348—Hydroxycarboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/4009—Two or more macromolecular compounds not provided for in one single group of groups C08G18/42 - C08G18/64
    • C08G18/4063—Mixtures of compounds of group C08G18/62 with other macromolecular compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4804—Two or more polyethers of different physical or chemical nature
    • C08G18/4812—Mixtures of polyetherdiols with polyetherpolyols having at least three hydroxy groups
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/622—Polymers of esters of alpha-beta ethylenically unsaturated carboxylic acids
    • C08G18/6245—Polymers having terminal groups containing active hydrogen
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/62—Polymers of compounds having carbon-to-carbon double bonds
    • C08G18/6216—Polymers of alpha-beta ethylenically unsaturated carboxylic acids or of derivatives thereof
    • C08G18/6262—Polymers of nitriles derived from alpha-beta ethylenically unsaturated carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/63—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers
    • C08G18/638—Block or graft polymers obtained by polymerising compounds having carbon-to-carbon double bonds on to polymers characterised by the use of compounds having carbon-to-carbon double bonds other than styrene and/or olefinic nitriles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/6505—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6511—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen the low-molecular compounds being compounds of group C08G18/32 or polyamines of C08G18/38 compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6603—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6607—Compounds of groups C08G18/42, C08G18/48, or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7614—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring
    • C08G18/7621—Polyisocyanates or polyisothiocyanates cyclic aromatic containing only one aromatic ring being toluene diisocyanate including isomer mixtures

Abstract

The present invention relates to a kind of preparation methods of multi-arm acrylate block copolymer, including step：The preparation of terminal hydroxy group acrylate macromole evocating agent, the preparation and multi-arm acrylate block copolymer of terminal hydroxy group acrylate block copolymer preparation.The beneficial effects of the invention are as follows：Multi-arm acrylate block copolymer is synthesized using ARGET ATRP methods, the Nomenclature Composition and Structure of Complexes of arm can be with accuracy controlling；The dispersibility that polymer is controlled by ATRP, makes block copolymer regularity greatly improve, improves the performance of product；Polymerisation can carry out in the space of opposing open, and the amount of catalyst is less than 500ppm, and product does not have to can be used directly except catalyst, and efficient, cost is low compared with conventional method；Arm is keyed on polyisocyanates using the reaction of hydroxyl and isocyanate group, is formed centered on polyisocyanates, acrylate block copolymer is the multi-arm structure of arm；Using arm first, process and realization difficulty simplify.

Description

A kind of preparation method of multi-arm acrylate block copolymer
Technical field
The invention belongs to chemical material fields, are related to a kind of preparation method of multi-arm acrylate block copolymer.
Background technology
Block copolymer is made of two or more different polymer segment of chemical constitution, according to composition The quantity of the monomeric species of block copolymer can be divided into two blocks, three block, more blocks etc..It can be by multiple polymers Advantageous property is combined together, and obtains the functional polymer material of performance comparative superiority.
There are many synthetic methods of block copolymer, including active anionic polymerization, living cationic polymerization, group transfer Polymerization, controllable/active free radical polymerization etc..Block copolymer is as a kind of special linear copolymer, with blend and grafting Copolymer is different in structure and in nature.Its glass transition temperature is determined by the lower polymer of temperature, and softening point But change with the higher polymer of the temperature, thus the wider range in elastomeric state.Block with specific structure Polymer can show the property different with the mixture of simple wire-form polymer and many random copolymers even homopolymer Matter can be used as thermoplastic elastomer, blending compatilizer, interface modifier etc..It is widely used in biological medicine, building, chemical industry etc. Every field all has great importance in theoretical research and practical application.
Multi-arm block copolymer refers to that one or more block copolymer chains are keyed to the same centronucleus by chemistry It is formed by polymer.Since the part of each arm can design its chain segment molecular weight and segment composition etc., greatly expand The type of block copolymer and diversity with performance add new content for the research of block copolymer.Its one is important Feature is that the linear polymer of ontology molecular weight identical with liquid viscosity ratio is much lower, it is possible to be widely used as flowing in coating Body conditioning agent, impact resistance dressing agent, contact adhesive and thermoplastic elastomer (TPE) etc..In addition it can also be used to that solubilizer, resistance to be blended Impact dressing agent, sealant and molding component etc..
ATRP methods synthesis multi-arm/star-type polymer is applied to quickly grow in recent years, star-type polymer in ATRP systems There are mainly three types of methods for synthesis：Divergent method, convergence method, microgel method.It can with the reactive carbon-halogen bond compound of more than two Star-type polymer is synthesized as initiator, arm number is determined that it is dense that brachium depends on initial monomer/initiator by the number for causing center Degree ratio.
Patent CN1486995 discloses the starlike dissaving polymer brush of one kind multi-arm containing polyhydroxy functional groups and its preparation side Method：Hyperbranched macromolecular initiator is first prepared, then atom transition free radical polymerization reaction in the presence of catalyst and ligand (ATRP) cause and polymerize containing double bond monomer, obtain the starlike dissaving polymer brush of multi-arm.It is more that patent CN101575402 discloses one kind Arm star polymer and preparation method thereof：It first prepares superbranched polystyrene macromole evocating agent, then causes the original of monomer Sub- transferring free-radical polymerization obtains multi-arm star polymer.
These methods may serve to synthesis multi-arm block polymer, and all be the macromolecular conduct of preparation structure complexity Initiator synthesizes multiarm polymers, belongs to core first, the relative complex realization of synthesis of hyperbranched macromolecular initiator Difficulty is relatively high.
The present invention utilizes the controllable advantage of ARGET ATRP, and first synthesis has the arm section that predetermined structure carries terminal hydroxy group, The part of arm can design chemical composition, molecular weight, block ratio etc..It recycles hydroxyl to be reacted with isocyanate group, successfully synthesizes Acrylate block copolymer with multi-arm structure.This method with it has been reported that method compare, belong to arm first, and Need not composite structure complexity hyperbranched macromolecular initiator, difficulty relative simplicity.
Invention content
The technical problem to be solved by the present invention is to：Based on the above issues, the present invention provides a kind of multi-arm arylate blocks The preparation method of copolymer.
The present invention solves a technical solution used by its technical problem：A kind of multi-arm acrylate block copolymer Preparation method, it is characterized in that：Include the following steps：
(1) preparation of terminal hydroxy group acrylate macromole evocating agent：By monomer I, initiator, complex liquid, reducing agent I and molten Agent I is added in reaction vessel, and for several times by the repetitive operation of reaction system vacuum nitrogen gas, 60~110 DEG C of reactions 0.5~10 are small When, terminal hydroxy group acrylate macromole evocating agent, molecular weight distribution is made<2.0；
(2) preparation of terminal hydroxy group acrylate block copolymer：In acrylate macromole evocating agent made from step (1) Monomer II, reducing agent II and solvent II is added, for several times by the repetitive operation of reaction system vacuum nitrogen gas, 60~110 DEG C of reactions 0.5~10 hour, terminal hydroxy group acrylate block copolymer, molecular weight distribution is made<2.0；
(3) preparation of multi-arm acrylate block copolymer：By terminal hydroxy group block copolymer solvent made from step (2) Catalyst and isocyanates is added in III dissolving, and 50~90 DEG C are reacted 1~9 hour, and multi-arm acrylate block copolymer is made.
Further, initiator is halogenated organic compound that an end group is hydroxyl in step (1), and initiator is specially Alpha-brominated isobutyric acid hydroxyl ethyl ester, alpha-chloro isobutyric acid hydroxyl ethyl ester, alpha-brominated isobutyric acid hydroxy butyl ester or alpha-chloro isobutyric acid hydroxy butyl ester In one kind.
Further, monomer I and monomer II are esters of acrylic acid, methyl acrylic ester, acrylate containing fluorine, contain One kind in methacrylate class, styrene or vinyl cyanide, monomer I and monomer II be specially butyl methacrylate, Methyl methacrylate, ethyl acrylate, butyl acrylate, Isooctyl acrylate monomer, methyl acrylate, dimethylaminoethyl acrylate methyl ammonia Base ethyl ester, trifluoroethyl methacrylate, Hexafluorobutyl mathacrylate, dodecafluoroheptyl methacrylate, styrene or third One kind in alkene nitrile；Complex liquid is stirred evenly for the transition metal halide, ligand and ethyl alcohol of oxidation state and is obtained at normal temperatures, oxygen The transition metal halide for changing state is CuCl2、CuBr2、FeCl3Or FeBr3In one kind, ligand be pentamethyl divinyl three Amine three-(N, N- dimethylaminoethyl) amine or 1, Isosorbide-5-Nitrae, one kind in 7,10,10- hexamethyl triens；I He of reducing agent Reducing agent II is one kind in stannous octoate, ascorbic acid or glucose.
Further, catalyst is one in dibutyl tin laurate, triethanolamine or stannous octoate in step (3) Kind, isocyanates is the addition product of diisocyanate or polyisocyanates and isocyanates, and isocyanates is specially diphenyl Methane diisocyanate, toluene di-isocyanate(TDI), isophorone diisocyanate, naphthalene -1,5- diisocyanate, 2,6-, bis- isocyanides Acid esters methyl caproate, hexamethylene diisocyanate, hexamethylene diisocyanate tripolymer, toluene di-isocyanate(TDI) and trihydroxy methyl Propane addition product or isophorone diisocyanate and one kind in pentaerythrite addition product.
Further, solvent I, solvent II and solvent III are toluene, methyl phenyl ethers anisole, N, N- bis- in step (1), (2) and (3) One kind in methylformamide, tetrahydrofuran, ethyl acetate or 1-Methyl-2-Pyrrolidone.
Further, monomer I：The molar ratio of initiator is 20：1~500：1, monomer II：Acrylate macromolecular causes The molar ratio of agent is 20：1~500：1, monomer I：The molar ratio of the transition metal halide of oxidation state is 1：0.0005~1： The transition metal halide of 0.00005 oxidation state：The molar ratio of reducing agent I or reducing agent II is 1：10~1：25, I dosage of solvent It is the 10~100% of I mass of monomer, II dosage of solvent is the 10~100% of II mass of monomer.
Further, hydroxyl rubs with isocyanate group in isocyanates in the terminal hydroxy group block copolymer in step (3) You are than being 1：1.0~1：1.5.
Further, in complex liquid oxidation state transition metal halide：The molar ratio of ligand is 1：10~1：30.
The beneficial effects of the invention are as follows：1. the present invention synthesizes multi-arm acrylic ester block using ARGET ATRP methods The Nomenclature Composition and Structure of Complexes of object, arm can be with accuracy controlling (molecular weight is controllable, narrow molecular weight distribution)；It is also possible to be controlled by ATRP The dispersibility of polymer processed makes block copolymer regularity greatly improve, to improve the performance of product；Polymerisation can be in phase To being carried out in open space, the amount of used catalyst is less than 500ppm, and product does not have to can be used directly except catalyst, efficiency Height, cost are low compared with conventional method；
2. arm is keyed on polyisocyanates by the present invention using the reaction of hydroxyl and isocyanate group, formed with polyisocyanate cyanogen Centered on acid esters, acrylate block copolymer is the multi-arm structure of arm；Different from the core first in report, present invention profit With arm first, compared with the core first method for the hyperbranched macromolecular initiator reported, process and realization difficulty letter Change.
Specific implementation mode
Presently in connection with specific embodiment, the invention will be further described, following embodiment be intended to illustrate invention rather than Limitation of the invention further.
Embodiment 1
(1) preparation of hydroxy terminated polypropylene acid butyl ester-b- polymethyl methacrylates (HO-PBA-b-PMMA), molecular weight It is 40600, structure is：
Wherein, m=200, n=150.
Butyl acrylate 60.00g, alpha-brominated isobutyric acid are added in the 500ml four-hole boiling flasks equipped with thermometer, agitating paddle Hydroxy butyl ester 0.5604g, CuBr20.04194g and pentamethyldivinyltriamine 0.6490g, Sn (EH)21.517g and solvent first Benzene 30.00g leads to nitrogen and is bubbled, react 210min under 70 DEG C of oil baths after mixing, and conversion ratio will be weighed up to after 82.7% Methyl methacrylate 35.16g well, toluene 18.00g and Sn (EH)21.138g is added with syringe in reaction bulb, reaction Stop after 255min, product is crossed into neutral alumina chromatographic column, removes the catalyst in polymer, methanol extraction after revolving, so It is placed in 50 DEG C of vacuum drying ovens and dries to constant weight, obtain product 79g, yield 83%.
(2) preparation of multi-arm PBA-b-PMMA
NCO/OH=1.0：1
Weigh HO-PBA-PMMA 20.00g, polyisocyanates (N3390 ,-NCO content 18%) 0.1149g, tin dilaurate Dibutyl tin 1 drips and toluene 40.00g is added in the four-hole boiling flask that agitating paddle, thermometer are housed, and is warming up to 80 DEG C, reacts 3 hours After stop, methanol extraction goes out polymer, and 50 DEG C of vacuum drying ovens are dried to constant weight, and product is obtained.
Embodiment 2
(1) preparation of hydroxy terminated polypropylene acetoacetic ester-b- polybutyl methacrylates (HO-PEA-b-PBMA), molecular weight It is 32000, structure is：
Wherein, m=200, n=85.
Ethyl acrylate 60.00g, alpha-brominated isobutyric acid are added in the 500ml four-hole boiling flasks equipped with thermometer, agitating paddle Hydroxy butyl ester 0.7173g, CuBr20.05369g and pentamethyldivinyltriamine 0.8308g, Sn (EH)21.942g and solvent first Benzene 30.00g leads to nitrogen and is bubbled, react 210min under 70 DEG C of oil baths after mixing, and conversion ratio will be weighed up to after 85% Methyl methacrylate 36.00g, toluene 18.00g and Sn (EH)20.8264g is added with syringe in reaction bulb, reaction Stop after 260min, product is crossed into neutral alumina chromatographic column, removes the catalyst in polymer, methanol extraction after revolving, so It is placed in 50 DEG C of vacuum drying ovens and dries to constant weight, obtain product 75g, yield 78%.
(2) preparation of multi-arm PEA-b-PBMA
NCO/OH=1.1：1
Weigh HO-PEA-b-PBMA 20.00g, Toluene-2,4-diisocyanate, 4- diisocyanate (TDI) 0.1197g, two fourth of tin dilaurate Base tin 1 drips and toluene 40.00g is added in the four-hole boiling flask that agitating paddle, thermometer are housed, and is warming up to 70 DEG C, after reacting 3.5 hours Stop, methanol extraction goes out polymer, and 50 DEG C of vacuum drying ovens are dried to constant weight, and product is obtained.
Embodiment 3
(1) preparation of the different monooctyl ester of hydroxy terminated polypropylene acid methyl esters-b- polyacrylic acid (HO-PMA-b-PEHA), molecular weight are 21000, structure is：
Wherein, m=100, n=68.
Methyl acrylate 60.00g, alpha-brominated isobutyric acid are added in the 500ml four-hole boiling flasks equipped with thermometer, agitating paddle Hydroxy butyl ester 1.668g, CuBr20.06251g and pentamethyldivinyltriamine 0.967g, Sn (EH)22.261g and solvent toluene 30.00g leads to nitrogen and is bubbled, react 250min under 70 DEG C of oil baths after mixing, and conversion ratio, will be load weighted up to after 81% Isooctyl acrylate monomer 86.57g, toluene 43.00g and Sn (EH)21.525g is added with syringe in reaction bulb, is reacted at 70 DEG C Stop after 300min, product is crossed into neutral alumina chromatographic column, removes the catalyst in polymer, methanol extraction after revolving, so It is placed in 50 DEG C of vacuum drying ovens and dries to constant weight, obtain product 103g, yield 70.2%.
(2) preparation of multi-arm PMA-b-PEHA
NCO/OH=1.2：1
Weigh HO-PMA-b-PEHA 20.00g, Toluene-2,4-diisocyanate, 4- diisocyanate-trimethylolpropane addition product (TDI- TMP adducts ,-NCO content 13%) 0.3692g, the drop of dibutyl tin laurate 1 and toluene 40.00g be added equipped with agitating paddle, In the four-hole boiling flask of thermometer, 80 DEG C are warming up to, reaction stops after 4.5 hours, and methanol extraction goes out polymer, 50 DEG C of vacuum drying ovens Drying obtains product to constant weight.
Embodiment 4
(1) preparation of hydroxy terminated polypropylene acid butyl ester-b- polyacrylonitrile (HO-PBA-b-PAN), molecular weight 10100, knot Structure is：
Wherein, m=50, n=70.
Butyl acrylate 60.00g, alpha-brominated isobutyric acid are added in the 500ml four-hole boiling flasks equipped with thermometer, agitating paddle Hydroxy butyl ester 2.242g, CuBr20.04200g and pentamethyldivinyltriamine 0.6499g, Sn (EH)21.519g and solvent first Benzene 30.00g leads to nitrogen and is bubbled, react 200min under 70 DEG C of oil baths after mixing, and conversion ratio will be weighed up to after 86% Acrylonitrile 34.69g, toluene 17.00g and Sn (EH)22.121g is added with syringe in reaction bulb, reacts 280min at 90 DEG C After stop, product is crossed into neutral alumina chromatographic column, removes the catalyst in polymer, methanol extraction after revolving is subsequently placed in It is dried to constant weight in 50 DEG C of vacuum drying ovens, obtains product 64g, yield 67.6%.
(2) preparation of multi-arm PBA-b-PAN
NCO/OH=1.3：1
Weigh HO-PBA-b-PAN 20.00g, isophorone diisocyanate-pentaerythrite addition product (- NCO content 15%) four-hole boiling flask equipped with agitating paddle, thermometer is added in 0.7207g, the drop of dibutyl tin laurate 1 and toluene 40.00g In, 80 DEG C are warming up to, reaction stops after 5.5 hours, and methanol extraction goes out polymer, and 50 DEG C of vacuum drying ovens are dried to constant weight, obtained Product.
Embodiment 5
(1) preparation of terminal hydroxy group polystyrene-b- polymethylacrylic acid trifluoro ethyl ester (HO-PS-b-PTFEMA), molecular weight It is 5100, structure is：
Wherein, m=20, n=18.
Styrene 60.00g, alpha-brominated isobutyric acid hydroxyl fourth are added in the 500ml four-hole boiling flasks equipped with thermometer, agitating paddle Ester 6.897g, CuBr20.05169g and pentamethyldivinyltriamine 0.7998g, Sn (EH)21.870g and solvent toluene 30.00g leads to nitrogen and is bubbled, react 360min under 110 DEG C of oil baths after mixing, and conversion ratio adjusts temperature up to after 80% To 75 DEG C, by load weighted trifluoroethyl methacrylate 87.12g, toluene 44.00g and Sn (EH)21.680g being added with syringe Enter in reaction bulb, stop after reacting 180min, product is crossed into neutral alumina chromatographic column, removes the catalyst in polymer, rotation Methanol extraction after steaming is subsequently placed in 50 DEG C of vacuum drying ovens and dries to constant weight, obtains product 102g, yield 69.3%.
(2) preparation of multi-arm PS-b-PTFEMA
NCO/OH=1.5：1
Weigh HO-PS-b-PTFEMA 20.00g, isophorone diisocyanate (IPDI) 1.308g, two fourth of tin dilaurate Base tin 1 drips and toluene 40.00g is added in the four-hole boiling flask that agitating paddle, thermometer are housed, and is warming up to 80 DEG C, after reacting 3.5 hours Stop, methanol extraction goes out polymer, and 50 DEG C of vacuum drying ovens are dried to constant weight, and product is obtained.
It is enlightenment with above-mentioned desirable embodiment according to the present invention, through the above description, relevant staff is complete Various changes and amendments can be carried out without departing from the scope of the technological thought of the present invention' entirely.The technology of this invention Property range is not limited to the contents of the specification, it is necessary to determine its technical scope according to right.

Claims (6)

1. a kind of preparation method of multi-arm acrylate block copolymer, it is characterized in that：Include the following steps：
(1) preparation of terminal hydroxy group acrylate macromole evocating agent：By monomer I, initiator, complex liquid, reducing agent I and solvent I It is added in reaction vessel, for several times by the repetitive operation of reaction system vacuum nitrogen gas, 60~110 DEG C are reacted 0.5~10 hour, Terminal hydroxy group acrylate macromole evocating agent, molecular weight distribution is made<2.0；
(2) preparation of terminal hydroxy group acrylate block copolymer：It is added in acrylate macromole evocating agent made from step (1) Monomer II, reducing agent II and solvent II, for several times by the repetitive operation of reaction system vacuum nitrogen gas, 60~110 DEG C of reactions 0.5~ 10 hours, terminal hydroxy group acrylate block copolymer, molecular weight distribution is made<2.0；
(3) preparation of multi-arm acrylate block copolymer：Terminal hydroxy group block copolymer made from step (2) is molten with solvent III Catalyst and polyisocyanates is added in solution, and 50~90 DEG C are reacted 1~9 hour, and multi-arm acrylate block copolymer is made；
Initiator is the halogenated organic compound that an end group is hydroxyl, and monomer I and monomer II are esters of acrylic acid, methyl-prop One kind in olefin(e) acid esters, acrylate containing fluorine, fluorine-containing methacrylate class, styrene or vinyl cyanide, complex liquid are Transition metal halide, ligand and the ethyl alcohol of oxidation state are stirred evenly and are obtained at normal temperatures, the transition metal halide of oxidation state For CuCl2、CuBr2、FeCl3Or FeBr3In one kind, ligand be pentamethyldivinyltriamine, three-(N, N- dimethylamino second Base) amine or 1, Isosorbide-5-Nitrae, one kind in 7,10,10- hexamethyl triens；Reducing agent I and reducing agent II are sad sub- One kind in tin, ascorbic acid or glucose, catalyst are one in dibutyl tin laurate, triethanolamine or stannous octoate Kind, polyisocyanates is toluene di-isocyanate(TDI) and trimethylolpropane addition product, isophorone diisocyanate and Ji Wusi One kind in alcohol addition product, solvent I, solvent II and solvent III are toluene, methyl phenyl ethers anisole, n,N-Dimethylformamide, tetrahydrochysene furan It mutters, one kind in ethyl acetate or 1-Methyl-2-Pyrrolidone.
2. a kind of preparation method of multi-arm acrylate block copolymer according to claim 1, it is characterized in that：Described Initiator is specially alpha-brominated isobutyric acid hydroxyl ethyl ester, alpha-chloro isobutyric acid hydroxyl ethyl ester, alpha-brominated isobutyric acid hydroxy butyl ester or alpha-chloro One kind in isobutyric acid hydroxy butyl ester.
3. a kind of preparation method of multi-arm acrylate block copolymer according to claim 1, it is characterized in that：Described Monomer I and monomer II are specially butyl methacrylate, methyl methacrylate, ethyl acrylate, butyl acrylate, acrylic acid Different monooctyl ester, methyl acrylate, dimethylaminoethyl methacrylate, trifluoroethyl methacrylate, methacrylic acid hexafluoro fourth One kind in ester, dodecafluoroheptyl methacrylate, styrene or acrylonitrile.
4. a kind of preparation method of multi-arm acrylate block copolymer according to claim 1, it is characterized in that：Described Monomer I：The molar ratio of initiator is 20：1~500：1, monomer II：The molar ratio of acrylate macromole evocating agent is 20：1~ 500：1, monomer I：The molar ratio of the transition metal halide of oxidation state is 1：0.0005~1：0.00005, the transition of oxidation state Metal halide：The molar ratio of reducing agent I or reducing agent II is 1：10~1：25, I dosage of solvent be I mass of monomer 10~ 100%, II dosage of solvent is the 10~100% of II mass of monomer.
5. a kind of preparation method of multi-arm acrylate block copolymer according to claim 1, it is characterized in that：Described The molar ratio of hydroxyl and isocyanate group in polyisocyanates is 1 in terminal hydroxy group block copolymer in step (3)：1.0~1： 1.5。
6. a kind of preparation method of multi-arm acrylate block copolymer according to claim 1, it is characterized in that：Described The transition metal halide of oxidation state in complex liquid：The molar ratio of ligand is 1：10~1：30.
CN201510347178.8A 2015-02-04 2015-06-19 A kind of preparation method of multi-arm acrylate block copolymer Active CN104892887B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
CN201510347178.8A CN104892887B (en) 2015-02-04 2015-06-19 A kind of preparation method of multi-arm acrylate block copolymer

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
CN2015100589735 2015-02-04
CN201510058973.5A CN104558495A (en) 2015-02-04 2015-02-04 Preparation method of polyurethane-grafted polyacrylate aqueous dispersion
CN201510347178.8A CN104892887B (en) 2015-02-04 2015-06-19 A kind of preparation method of multi-arm acrylate block copolymer

Publications (2)

Publication Number Publication Date
CN104892887A CN104892887A (en) 2015-09-09
CN104892887B true CN104892887B (en) 2018-07-17

Family

ID=53075634

Family Applications (5)

Application Number Title Priority Date Filing Date
CN201510058973.5A Withdrawn CN104558495A (en) 2015-02-04 2015-02-04 Preparation method of polyurethane-grafted polyacrylate aqueous dispersion
CN201510306733.2A Expired - Fee Related CN104861151B (en) 2015-02-04 2015-06-06 A kind of preparation method of polyurethane polyureas methyl methacrylate segmented copolymer
CN201510306786.4A Pending CN104892805A (en) 2015-02-04 2015-06-06 Preparation method of polyurethane grafted polystyrene aqueous dispersion
CN201510306669.8A Expired - Fee Related CN104861147B (en) 2015-02-04 2015-06-06 A kind of preparation method of polyurethane grafting polyacrylic acid ester aqueous dispersion
CN201510347178.8A Active CN104892887B (en) 2015-02-04 2015-06-19 A kind of preparation method of multi-arm acrylate block copolymer

Family Applications Before (4)

Application Number Title Priority Date Filing Date
CN201510058973.5A Withdrawn CN104558495A (en) 2015-02-04 2015-02-04 Preparation method of polyurethane-grafted polyacrylate aqueous dispersion
CN201510306733.2A Expired - Fee Related CN104861151B (en) 2015-02-04 2015-06-06 A kind of preparation method of polyurethane polyureas methyl methacrylate segmented copolymer
CN201510306786.4A Pending CN104892805A (en) 2015-02-04 2015-06-06 Preparation method of polyurethane grafted polystyrene aqueous dispersion
CN201510306669.8A Expired - Fee Related CN104861147B (en) 2015-02-04 2015-06-06 A kind of preparation method of polyurethane grafting polyacrylic acid ester aqueous dispersion

Country Status (1)

Country Link
CN (5) CN104558495A (en)

Families Citing this family (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104558495A (en) * 2015-02-04 2015-04-29 常州大学 Preparation method of polyurethane-grafted polyacrylate aqueous dispersion
CN105199050B (en) * 2015-09-11 2018-06-08 湘潭大学 A kind of polyurethane grafted copolymer and preparation method thereof
CN105601828A (en) * 2015-12-19 2016-05-25 高明志 Castor-oil-based polyurethane-acrylate emulsion preparation method
CN106467591B (en) * 2016-09-06 2019-02-12 常州大学 A kind of synthetic method of the cyclic polymer containing polycyclic and linear segment
CN106751070A (en) * 2016-12-16 2017-05-31 安徽亚兰密封件有限公司 A kind of low temperature resistant modified rubber seal of high tenacity and preparation method thereof
CN106750057A (en) * 2017-01-10 2017-05-31 上海鲁聚聚合物技术有限公司 A kind of styrene fluorine-containing ester block copolymer and preparation method thereof
CN109206570B (en) * 2017-06-30 2023-04-25 厦门天策材料科技有限公司 Flexible physical split-phase supermolecular dynamic polymer and application thereof
CN107629673B (en) * 2017-09-28 2021-01-08 宁波帅特龙集团有限公司 High-strength coating material and coating process thereof
CN107694868B (en) * 2017-09-28 2021-01-19 宁波帅特龙集团有限公司 Coating process of automotive interior trim part
CN108047367B (en) * 2017-11-13 2020-09-11 四川大学 Fluorine-containing polyacrylate dihydric alcohol and preparation method thereof
CN107903348B (en) * 2017-11-28 2020-06-26 常州大学 Preparation method of polyethylene glycol grafted polymethyl methacrylate amphiphilic graft copolymer
CN107880229B (en) * 2017-12-08 2020-12-15 万华化学集团股份有限公司 Preparation method of end group modified polyacrylate block copolymer and polyacrylate block copolymer prepared by preparation method
CN108467471B (en) * 2018-04-04 2020-10-30 优美特（北京）环境材料科技股份公司 Comb-shaped multi-branched aqueous polyurethane dispersion and preparation and application thereof
CN108409993B (en) * 2018-04-19 2020-02-21 南通纺织丝绸产业技术研究院 Fluorine-containing polycaprolactone film and preparation method thereof
CN108484922B (en) * 2018-04-19 2019-10-29 苏州大学 A kind of hydrophobic type polycaprolactone and preparation method thereof
CN108676141A (en) * 2018-05-25 2018-10-19 北京化工大学 Using polystyrene as the block polyurethane preparation method of hard section
CN109134745B (en) * 2018-08-21 2021-06-01 深圳市广业电子科技有限公司 Solvent-free polymerization production technology for preparing (methyl) acrylic acid-polyester block copolymer
CN109810224B (en) * 2019-01-24 2020-06-09 中国石油大学(北京) Initiation system of electron transfer activation regeneration catalyst and gelling time control method
CN110407994A (en) * 2019-06-20 2019-11-05 宜兴鸿兴瑞奇新材料科技有限公司 The preparation method of a kind of environment-friendly water-based polyurethane indoor decoration synthetic leather and its resin dedicated
CN110845738A (en) * 2019-11-28 2020-02-28 科迈特新材料有限公司 Proportioning process for processing high-molecular synthetic material
CN110982035A (en) * 2019-12-11 2020-04-10 上海三恩化工有限公司 Aqueous polyurethane for flocking adhesive and preparation method thereof
CN111423558A (en) * 2020-05-26 2020-07-17 福建华夏蓝新材料科技有限公司 Preparation method of self-extinction aqueous polyurethane dispersion
CN112375174A (en) * 2020-09-22 2021-02-19 苏州双象光学材料有限公司 Preparation method of PMMA material particles for injection molding light guide plate
CN113292684B (en) * 2021-05-28 2022-08-05 万华化学集团股份有限公司 Modified polymethyl methacrylate and preparation method thereof

Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1486995A (en) * 2003-07-31 2004-04-07 上海交通大学 Multiple-arm star-shaped super-branched polymer brush with several hydroxy groups and its prepn process
CN101575402A (en) * 2009-05-31 2009-11-11 中国科学院化学研究所 Multi-arm star-type polymer and preparation method thereof
CN101921380A (en) * 2010-02-05 2010-12-22 江苏工业学院 Polyacrylate-urethane copolymer and preparation method thereof
CN104031224A (en) * 2014-06-16 2014-09-10 常州大学 Preparation method of polyacrylate-polyurethane thermoplastic elastomer
CN104231898A (en) * 2014-09-11 2014-12-24 常州大学 Star-shaped acrylate resin high-solid coating and preparation method thereof

Family Cites Families (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS5911894B2 (en) * 1976-11-16 1984-03-19 王子製紙株式会社 photosensitive composition
US4264755A (en) * 1976-11-19 1981-04-28 Mobay Chemical Corporation Hydroxy-functional vinyl copolymers
CN101445579A (en) * 2008-12-11 2009-06-03 东华大学 Preparation method of a polyurethane macromer HPU/styrene (St) interpenetrating polymer network composite material
CN102604029B (en) * 2012-02-22 2014-05-28 常州大学 Fluorine-containing waterborne polyurethane (PU) and preparation method thereof
CN104558495A (en) * 2015-02-04 2015-04-29 常州大学 Preparation method of polyurethane-grafted polyacrylate aqueous dispersion

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1486995A (en) * 2003-07-31 2004-04-07 上海交通大学 Multiple-arm star-shaped super-branched polymer brush with several hydroxy groups and its prepn process
CN101575402A (en) * 2009-05-31 2009-11-11 中国科学院化学研究所 Multi-arm star-type polymer and preparation method thereof
CN101921380A (en) * 2010-02-05 2010-12-22 江苏工业学院 Polyacrylate-urethane copolymer and preparation method thereof
CN104031224A (en) * 2014-06-16 2014-09-10 常州大学 Preparation method of polyacrylate-polyurethane thermoplastic elastomer
CN104231898A (en) * 2014-09-11 2014-12-24 常州大学 Star-shaped acrylate resin high-solid coating and preparation method thereof

Also Published As

Publication number Publication date
CN104558495A (en) 2015-04-29
CN104861151A (en) 2015-08-26
CN104861151B (en) 2017-09-08
CN104892887A (en) 2015-09-09
CN104861147B (en) 2017-08-01
CN104861147A (en) 2015-08-26
CN104892805A (en) 2015-09-09

Similar Documents

Publication Publication Date Title
CN104892887B (en) A kind of preparation method of multi-arm acrylate block copolymer
CN1845944A (en) Mixtures for producing reactive hot melt adhesives and reactive hot melt adhesives obtained on the basis thereof
CN106832157B (en) One kind is containing fluorine-containing three block acrylate copolymer of POSS and preparation method thereof
CN103261236B (en) Curable compositions with moisture-urable functionality clusters near the chain ends
Wever et al. Comb-like thermoresponsive polymeric materials: Synthesis and effect of macromolecular structure on solution properties
CN102216356B (en) Process for preparing AB diblock copolymers with a broadly distributed a block
Wang et al. Reversible coordinative chain transfer polymerization of isoprene and copolymerization with ε-caprolactone by neodymium-based catalyst
CN104755506A (en) Controlled radical polymerization of (meth)acrylic monomers
CN101792503B (en) Fluorinated acrylate atom transfer radical polymerization (ATRP) macromolecule initiator as well as preparation method and application thereof
WO2014099748A1 (en) Process of controlled radical polymerization of branched polyacrylates
US11498984B2 (en) Method for preparing vinyl ether polymer by photo-initiated polymerization
CN108707442A (en) Adhesive composition and bonding sheet
Antoun et al. Lithium diisopropylamide as initiator for the anionic polymerization of methacrylates
CN103998518A (en) Highly functionalized resin blends
CN107216419B (en) It is a kind of to prepare high concentration hydroxyl polyacrylic resin and its cured method
CN102209736A (en) Method for producing aba-triblock copolymers with a widely distributed b-block
US8883941B2 (en) Methods and apparatus for controlled single electron transfer living radical polymerization
Karatzas et al. Synthesis of well-defined functional macromolecular chimeras based on poly (ethylene oxide) or poly (N-vinyl pyrrolidone)
CN107903348B (en) Preparation method of polyethylene glycol grafted polymethyl methacrylate amphiphilic graft copolymer
Wang et al. Hybrid Acrylic‐Polyurethane Latexes by Miniemulsion Polymerization
CN103374108A (en) Preparation method of triblock acrylic acid ester thermoplastic elastomer
CN103739833B (en) A kind of method preparing polylactide
CN101885816B (en) Method for preparing poly(styrene-b-acrylonitrile) by two-step polymerization method
CN102209737A (en) Method for producing telechelics having a wide molecular weight distribution
Jang et al. Molecular recognition properties of biodegradable photo-crosslinked network based on poly (lactic acid) and poly (ethylene glycol)

Legal Events

Date Code Title Description
C06 Publication
PB01 Publication
C10 Entry into substantive examination
SE01 Entry into force of request for substantive examination
GR01 Patent grant
GR01 Patent grant